Levelling agents for dyeing textile materials



United States Patent LEVELLING AGENTS FOR DYEIN G TEXTILE MATERIALSFranz Laudauer and Gerhard Weckler, Frankfurt am Main, and MartinRenter, Kronberg, Taunus, Germany, assignors to Farbwerke HoechstAktiengeseiischaft vormals Meister Lucius & Bruning, Frankfurt am Main,Germany, a corporation of Germany No Drawing. Fiied Nov. 2, 1964, Ser.No. 403,418 Claims priority, application Germany, Nov. 2, H63,

7 Claims. (Ci. 8-35) In the dyeing with leuco-sulfuric acid esters ofvat dyestuffs difficulties are often caused by the fact that the leucocompounds of quite a number of vat dyestuffs show a great afiinity tocellulose fibers and that unlevelled dyeings are obtained due to thehigh velocity with which the dyestuffs are, therefore, absorbed by thefibers. In many cases, difliculties of said kind are likewise observedwith substantive dyestuffs as well as in the dyeing ofnitrogencontaining fibers dyeable with acid dyestuffs, for instance,with wool dyestutfs absorbed by the fibers in a neutral or a weakly acidmedium.

It is already known that by adding to the dyebaths cationic compounds onthe base of polyalkylene-polyamines the absorption period is increasedand the evenness of the dyeings is improved. In many cases, however,this method of operation shows the drawback that the addition compoundsformed between the dyestutf and the auxiliary agent are very stable andthat in the course of the dyeing process the dyestulf is onlyinsufiiciently liberated, even if the temperature is increased so thatconsiderable amounts of dyestutf are lost for the dyeing process. Theknown oxethylated alkyl-phenols or the oxethylated fatty alcoholsrecommended as additional agents for obtaining more even dyeings showsimilar drawbacks. Likewise with these products the complexes formed inthe dyebath between the dyestuft and the auxiliary agent are often of ahigh stability so that large amounts of dyestufi are lost for the dyeingprocess and that only pale shades are obtained.

Now we have found that said diificulties could be overcome and that withfull exhaustion of the dyebaths more even dyeings were obtained onnitrogen-containing fibers and on cellulose fibers by adding to thedyebaths watersoluble oxazolines carrying in 4-position polyglycol etherchains and in 2-position-directly or by means of a bridge-member-anal'kyl radical containing about 4-20 carbon atoms, or by treating thedyeings additionally with an aqueous bath containing such an oxazolinecompound. It is likewise of advantage that the levelling agentsaccording to the invention are active in the same way for dyeings onnitrogen-containing fibers as well as on cellulose fibers, whereas mostof the hitherto known levelling agents are suitable for dyeings oneither one or the other kind of fibers.

The oxazoline compounds used as levelling agents according to theinvention are, above all, those corresponding to the general formula in.which R represents an alkyl radical with 320, preferably 618 carbonatoms,A stands for a methylene group, for oxygen or the sulfur atom, Rstands for an alkyl group with.1'4 carbon atoms or the radical 'icewherein n is an integer of 2 or 3, y=1-3, preferably 1, x=4-100,preferably 960, R represents the radical wherein n, y and x have themeanings given above.

As oxazolines substituted in the above-mentioned way, there are used,for instance, the addition compounds of ethylene oxide and/ or propyleneoxide to 2-hexyl-4-methyl 4-hydroxy-methyl-oxazoline,2,-undecyl-4-ethyl-4-hydroxy-methyl-oxazoline,Z-heptadecyl-4-ethyl-4-hydroxymethyl-oxazolineorZ-undecyl-4,4abis-hydroxy-methyloxazoline. The oxazolines can beprepared according to known methods, for instance, according to US.Patent 2,504,951 from saturated or unsaturated monocarboxylic acids,such, for instance, as tallow oil fatty acid or coconut oil fatty acid,by reaction with alkylol-amines-( 1,2) containir; at least 2 hydroxygroups, such, for instance, as 2 amino-Z-ethyl-propanediol-(1,3),Z-amino-Z-methyl-propanediol-(L3) or thetris-hydroxy-methyl-aminomethane with splitting ofi of 2 mols of waterat an elevated temperature and, if desired, under reduced pressure. Thehydroxy groups of the substituted oxazolines thus obtained can then bereacted according to known methods, for instance, according to theoperating method described in German patent application No. 1,027,672laid open to public inspection, with epoxides, such, for instance, asethylene-oxide, or propylene-oxide or mixtures of said epoxides. Whenoperating in this manner, about 4-100 mols of epoxide, preferably 9-60mols, are used per mol of oxazoline.

In compliance with the dyeing method, the dyestuffs used and the fibrousmaterial to be treated, the oxazoline compounds used as levelling agentsaccording to the inveution are used in varying quantities. The mostfavorable amount for each treatment can be easily ascertained .by adyeing test.

Generally, quantities Within a range of about 0.05 and about 8grams/liter, preferably between 0.1 and 3 grams/ liter of dyebath areused.

The oxazoline compounds claimed are likewise excellently suitable forthe additional levelling of unequal dyeings. When operatingin this way,the dyeings are additionally treated at an elevated temperature with anaqueous bath containing the oxazoline compound generally under the sameconditions under which the dyeing is carried-outQ v The levelling agentsaccording to the invention can be applied together with the usualdyestuffs, for the levelling of all dyeings realized onnitrogen-containing fibers and cellulose fibers according to knowndyeing methods. Nitrogen-containing fibers comprise polyamide fibers,above all protein fibers, such as wool and silk. Most suitable for thedyeing of said nitrogen-containing fibers are, above all, those of theseries of the so-called acid dyestulfs. As cellulose fibers there areused native and regenerated cellulose fibers. As dyestuffs which may beused for the dyeing of cellulose fibers there are mentioned, forinstance, substantive dyestuifs and vat dyestufis which are used in theform of their sodium-leuco compounds.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto. Unless otherwise stated, theindications in percent are calculated on the weight of the goods to bedyed.

Example 1 Bleached cotton yarn is dyed in the open vat at agoodsto-liquor ratio of 1:20 with 2% of the dyestuff C.I.7O 305 (Cf.Colour Index, 2nd edition (1956)), according to the lN-process for 45minutes at 5060 C. Per liter of dyebath 16 cc. of sodium hydroxidesolution (38 B.) and 3 grams of sodium-dithionite are used. The goods =3are then achieved in the normal way, i.e. the dyeing is subjected in theusual way to oxidation, acidification and saponification. 5 grams of thecotton yarn thus dyed together with 5 grams of undyed cotton yarn aretreated in the same manner as described above with the blank vat IN. Acompletely unsatisfactory levelling effect is obtained together with avery uneven dyeing of the added yarn. Likewise insufficient levellingeffects are obtained by adding in each case 0.1 or 1.5 g./l. ofpolyglycol of an average molecular weight of 1000 or 0.1 or 1.5 g./l. ofthe addition compound of mols of ethylene-oxide to 1 mol of dodecylalcohol. In the same manner levelling effects are realized bysimultaneously using in each case 0.1 or 1.5 g./l. of the additioncompound of mols of ethylene-oxide to 1 mol ofZ-undecyl-4,4-bis-hydroxymethyloxazoline. Already with low startingquantities a distinct levelling effect is observed together with animproved evenness of the dyeing, but no remarkable retardation effectoccurs. Only with quantities of 1.5 g./l.

and more a retardation effect can gradually be observed. 7

Example 2 On the same material and in the same Way as described inExample 1 a dyeing is produced with 2% of the dyestulf C.I.6O 010 (cf.Colour Index, 2nd edition (1956)) according to the .IN-process andlevelling tests are then carried out as described in Example 1.

Whereas again with the blank vat IN and products such as a polyglycol ofa molecular weight of 600 and an addition product of 5 mols ofethylene-oxide to 1 mol of oleyl alcohol in quantities of 0.1 or 1.5g./l. each, a completely insufficient levelling effect is obtained, verygood levelling effects without remarkable retarding action are observedwhen starting from 0.1 or 0.5 g./l. of the addition compound of 9 molsof ethylene-oxide to 1 mol of 2-undecyl-4,4-bis-hydroxy-methyloxazoline.Similar results are obtained with 0.1 to 0.5 g./l. of the additionproduct of 53 mols of ethylene-oxide to 1 mol of2-undecyl-4-ethyl-4-hydroxy-methyl-oxazoline.

Example 3 As described in Example 1, a dyeing is obtained with 2% of thedyestuff C.I.59800 (cf. Colour Index, 2nd edition (1956)) according tothe IN-process and levelling tests are likewise carried out as describedin Example 1. With the blank IN-vat and compounds such as the additioncompound of 15 mols of ethylene-oxide to 1 mol of stearyl alcohol orpolyglycol of a molecular weight of 600 in quantities of 0.1 or 1.5g./l. in each case, a completely unsatisfactory result is obtained,whereas with 0.1

or 0.5 g./l. in each case of the addition compound of 12 mols ofethylene-oxide to 1 mol of 2-undecyl-4-ethyl- 4-hydroxy-methyl-oxazolinea good levelling effect is obtained.

Example 4 10 weight units of a Wool gabardine (20 grams) are dividedinto a larger piece of 4 Weight units (8 g.) and into 6 smaller piecesof 1 Weight unit (2 grams) each, thoroughly Wetted and then centrifugedin a uniform way. The large piece of 4 weight units is first introducedinto the boiling dyebath containing 1% of the wool dyestuif C.I.24 800(cf. Colour Index, 2nd edition (1956)), 5% of sodium sulfate and 4% ofacetic acid. After 2, 4, 8, 16, 32 and 64 minutes each a small piece ofa weight-unit of one is added and boiling is continued for a further 56minutes, after the last piece has been added. Total boiling time: 2hours. The goods-to-liquor ratio amounts to 1:40 calculated on the totalwool material (:800 cc.). Evaporated water is replaced after a boilingtime of 1 hour. (Kramrisch test, B. Kramrisch, J. 502. Dyers and Coll.,May 1959, pages 242 et seq.)

The above-described combined absorption-levelling test is carried outwithout as Well as with addition of increasing quantities of thecompounds claimed.

Whereas without the addition of the auxiliary agents the dyestuff isnerly completely absorbed prior to the addition of the last pieces ofthe wool gabardine, a good levelling effect between the Wool piecesadded at first to the dyebath and those added at last can be observed,if in each case 0.1 or 2 g./l. of the addition compound of 12 mols ofethylene-oxide to 1 mol of 2-undecyl-4-ethyl- 4-hydroxymethyl-oxazolineare added in low concentrations.

A similar good levelling effect is obtained with the compounds mentionedin Examples -1-3, whereas products such as polyglycols of a molecularweight of 1000 as well as an addition product of 5 mols of ethyleneoxideto 1 mol of oleyl alcohol in quantities of 0.1. or 2 g./l. only show asmall levelling effect.

Example 5 A previously cleaned cross-wound bobbin (as described inExample 1) is dyed at a goods-to-liquor ratio of 1:10 in the closedapparatus with 0.2% of the dyestuff C.I.70 035 (cf. Colour Index, 2ndedition (1956)) according to the IN-process in the usual manner for 45minutes at 50-60 C. Per liter of dyebath 20 cc. of sodium hydroxidesolution (38 B.) and 4.5 grams of sodium-dithionite are used. The bobbinis badly dyed through and the dyeing is unlevelled.

In the same manner, but with addition of 0.5 g./l. of the additioncompound of 20 mols of ethylene-oxide to 1 mol of2-undecyl-4,4-bis-hydroxy-methyl-oxazoline a bobbin is dyed. A bobbin isobtained which is well dyed through.

Example 6 10 grams of loose wool are dyed for 1 hour at C. and at agoods-to-liquor ratio of 1:40 with a mixture consisting of 0.3% of thedyestuff C.I.42 655 0.4% of the dyestuff C.I.24 825 0.2% of the dyestuffC.I.18 (cf. Colour Index, 2nd

edition (1956)) while adding 5% of sodium sulfate and 2% of acetic acidof 30% strength.

A completely uneven dyeing is obtained.

In the same manner, but with addition of 0.5% of the addition compoundof 12 mols of ethylene-oxide and 1 mol of2-undecyl-4-ethyl-4-hydroxy-methyl-oxazoline the dyeing shows aconsiderably increased evenness.

We claim:

1. Process for producing even dyeings on nitrogen containing fibers andon cellulose fibers by adding to the dyebath a levelling agent of theformula wherein R represents an alkyl radical containing 3-20 carbonatoms, A stands for a member seleced from the group consisting of themethylene radical, oxygen and sulfur atom, R stands for a memberselected from the group consisting of an alkyl group containing 1-4carbon atoms and a radical (CH (C H O) H, wherein n is an integer of 2to 3, y is an integer of 1 to 3 and x is an integer of 4-100, Rrepresents the radical (CH (C I-I ,,O) H, wherein n, y and x have themeanings given above.

2. The process as claimed in claim 1, wherein the levelling agent isadded to the dyebath in quantities within the range of 0.05 to 8 gramsper liter.

wherein R represents an alkyl radical containing 3-20 carbon atoms, Astands for a member selected from the group consisting of the methyleneradical, oxygen and sulfur atom, R stands for a member selected from thegroup consisting of an :alkyl group containing 1-4 carbon atoms and aradical (CH -(C H O) H, wherein n is an integer of 2 to 3, y is aninteger of 1 to 3 and x is an integer of 4-100, R represents the radical(CH (C I-I O) H, wherein n, y and x have the meanings given above.

4. The process as claimed in claim 3, wherein the aqueous solutioncontains the levelling agent in quantities within the range of 0.05 to 8grams per liter.

5. A process as claimed in claim 1, wherein the addition compound of 20mols of ethylene-oxide to 1 mol of Z-undecyl 4,4-bishydroxymethyloxazoline is used as levelling agent.

6. A process as claimed in claim 1, wherein the addition compound of 12mols of ethylene-oxide and 1 mol of2-undecyl-4-ethyl-4-hydroxy-methyl-oxazoline is used as levelling agent.

7. In a process for dyeing nitrogen containing fibers and cellulosefibers to obtain even dyeings, the improve- 6 ment comprising: adding tothe dyebath a levelling agent of the formula:

/Ra N CRa R,-A-o CH3 0 wherein R is an alkyl radical containing 3 to 20carbon atoms, A is a member selected from the group consisting of themethylene radical, oxygen and sulfur atoms;

R is a member selected from the group consisting of an alkyl groupcontaining 1 to 4 canbon atoms and a radical (CH (C H O) H, wherein n isan integer of 2 to 3, y is an integer of 1 to 3 and x is an integer of 4to R is the radical (CH C I-I O) H, wherein n, y

and x have the meanings given above.

References Cited by the Examiner UNITED STATES PATENTS 2,187,823 1/1940Ulrich et a1 8-88 X 3,096,139 7/1963 Hindle 888 X 3,097,046 7/1963Walles et al 888 3,223,471 12/1965 Kuth et al 8-88 FOREIGN PATENTS1,027,672 4/1958 Germany.

OTHER REFERENCES A. M. Schwartz et al.: Surface Active Agents andDetergents, vol. II, 1958, pp. and 111, pub. by Interscience PublishersInc., New York, NY.

NORMAN G. TORCHIN, Primary Examiner.

J. T. HERBERT, Assistant Examiner.

1. PROCESS FOR PRODUCING EVEN DYEINGS ON NITROGEN CONTAINING FIBERS ANDON CELLULOSE FIBERS BY ADDING TO THE DYEBATH A LEVELING AGENT OF THEFORMULA